Glycidyl sulfonamide compound

ABSTRACT

A novel glycidyl sulfonamide compound having a (poly)siloxane main chain of its molecule is used alone or in admixture with an epoxy resin to give a cured material being excellent in flexibility, elongation and impact strength without deteriorating thermal resistance, chemical resistance and water absorption thereof. An epoxy resin composition or a resin composition for an epoxy paint containing a glycidyl sulfonamide compound, the epoxy resin and a curing agent for epoxy resin provides a cured material or a coating film having the above-mentioned excellent properties. A process for preparing a glycidyl sulfonamide compound characterized in that subjecting an amine modified silicone having a (poly)siloxane main chain of its molecule to condensation reaction with a sulfonyl chloride to give a sulfonamide compound, which is subjected to an addition reaction with an epihalohydrin to give the glycidyl sulfonamide compound.

BACKGROUND OF THE INVENTION

The present invention relates to (1) a novel glycidyl sulfonamidecompound which is a liquid compound having a low viscosity and whichprovides a cured material having excellent flexibility and elongation,and more particularly to a glycidyl sulfonamide compound having siloxaneor polysiloxane (hereinafter referred to as "(poly)siloxane") main chainin its molecule, and a process for preparing the same, (2) an epoxyresin composition comprising the glycidyl sulfonamide compound whichprovides a cured material having high thermal resistance and excellenttoughness, and (3) a cured material prepared by curing the composition,and more particularly to an epoxy resin composition for epoxy paintswhich provides a coating film being excellent in flexibility and surfaceproperties and a coating film formed by curing the composition.

Epoxy resins have been widely used for various purposes such as resinsfor paints, materials for electric apparatuses, adhesive agents, coatingmaterials, materials used in civil engineering and construction industryand matrix materials for FRP because the epoxy resins have excellentproperties such as thermal resistance, chemical resistance, adhesiveproperties and electrical insulating property. Especially, among theepoxy resins, an epoxy resin having at least one N,N-diglycidylaminogroup in its molecule (hereinafter referred to as "glycidylamine epoxyresin"), an epoxy resin which is prepared by means of a condensationreaction of a bisphenol with an epihalohydrin (hereinafter referred toas "epi-bis type epoxy resin"), and the like are used as adhesive agentshaving thermal resistance and matrix materials for prepreg used inspacecraft and aircraft since the cured materials prepared by curingwith heat the epoxy resins together with curing agents exhibit both highthermal resistance and excellent adhesive property for a substrate.

However, generally, the cured epoxy resin does not have sufficientflexibility, toughness, impact strength, and the like, and does notsufficiently satisfy the mechanical properties required in various uses.Especially, a coating film of the epoxy resin does not sufficientlysatisfy the mechanical properties required for paints.

In order to improve the mechanical properties of the epoxy resin such asflexibility and elongation, many attempts such as adding a flexibilizerto usual epoxy resin compositions in order to decrease the stress of thecured material prepared from the resin compositions and adding a fillerto the compositions have been made.

Examples of the flexibilizer are, for instance, glycidyl compoundprepared from oxyalkylene or polyoxyalkylene such as butanedioldiglycidyl ether, glycerol triglycidyl ether, trimethylolpropanetriglycidyl ether, polypropylene glycol diglycidyl ether (available fromASAHI DENKA KOGYO K. K. under the trade name of "ED-506", DAINIPPON INKAND CHEMICALS, INC. under the trade name of "Epiclon 707", and thelike), polyethylene glycol diglycidyl ether (available from Nippon Oiland Fats Co., Ltd. under the trade name of "Epiol E-100"). Theseflexibilizers are used as reactive diluents. However, theseflexibilizers have the defects that the amount of the flexibilizersshould be adjusted to 5 to 20 parts by weight (hereinafter referred"parts by weight" to as "parts") because the properties of the epoxyresin by adding flexibilizers cannot be sufficiently exhibited when theamount is without the range of 5 to 20 parts. Accordingly, the thermalresistance of the cured material of the resin is considerably decreased.

Further, these glycidyl compounds prepared from alkylene ether orpolyalkylene ether have the defects that when these compounds areco-cured with an epoxy resin, the obtained cured materials or coatingfilms exhibit a deteriorated thermal resistance and chemical resistance,or an higher water absorption since these compounds have an etherlinkage in the main chain of its molecule.

On the other hand, it is known that (poly)siloxane is remarkablyexcellent in thermal resistance, weatherability and oxidationdeterioration resistance compared with (poly)ether because Si--O linkagehas larger bonding energy than C--O linkage. The (poly)siloxane which iswell-known as silicon oil is also excellent in water repellency,hydrophobic property and electric property, while the (poly)etherexhibits water absorption. The (poly)siloxanes are widely used asheating medium, lubricating oil, and the like because the(poly)siloxanes have the above properties. For instance, a process inwhich a silicone rubber having a good stability against oxidation isblended or dispersed into an epoxy resin is proposed (JapaneseUnexamined Patent Publication No. 21417/1983). However, it is known that(poly)siloxane has a defect that the (poly)siloxane is bled on thesurface of the cured resin due to thermal history when the(poly)siloxane is merely blended and dispersed into an epoxy resin since(poly)siloxane is essentially poor in compatibility with as epoxy resin(Japanese Unexamined Patent Publication No. 116654/1987).

A process in which various rubber modifiers such as carboxyl groupterminated butadiene-acrylonitrile rubber (CTBN) and amino groupterminated butadiene-acrylonitrile rubber (ATBN) are added into an epoxyresin to form a cured material of which structure is like seas andislands in order to control the thermal resistance of the cured epoxyresin, is also proposed (refer to "Shin-epokishi-jushi" (new epoxyresin) edited by Hiroshi Kakiuchi and published by Shoko-do, and thelike). These rubber modifiers, however, have a defect that long-termheat resistance of the cured material of the resin containing themodifiers is deteriorated because the rubber modifiers are very poor inoxidation resistance.

From the viewpoints mentioned above, a novel flexibilizer which impartsflexibility to cured materials or coating films of the epoxy resinwithout deteriorating the properties of the cured material or coatingfilm of the resin, particularly, without increasing the waterabsorption, has been desired.

An object of the present invention is to provide a glycidyl compoundwhich can be co-cured with an epoxy resin to give a cured material or acoating film having excellent toughness, flexibility and elongation,without largely deteriorating the thermal resistance of the cured epoxyresin.

These and other objects of the invention will be apparent to one skilledin the art upon consideration of the following description and appendedclaims.

SUMMARY OF THE INVENTION

It has now been found that a glycidyl sulfonamide compound having a(poly)siloxane main chain in its molecule can satisfy theabove-mentioned purpose.

That is, in accordance with the present invention, there is provided aglycidyl sulfonamide compound (hereinafter referred to as "glycidylsulfonamide compound (A)") which has a (poly)siloxane main chain in itsmolecule and which can be co-cured with an epoxy resin to give a curedmaterial or a coating film of the epoxy resin having excellenttoughness, flexibility, elongation and impact strength without largelydeteriorating the properties such as thermal resistance, chemicalresistance and water absorption, and a process for preparing theglycidyl sulfonamide compound (A). Further, in accordance with thepresent invention, there is provided an epoxy resin composition, thatis, a resin composition for epoxy paint containing the glycidylsulfonamide compound (A) and a cured material, particularly a coatingfilm formed by curing the composition.

BRIEF EXPLANATION OF THE DRAWINGS

FIGs. 1, 2 and 3 are diagrams showing the results of infrared absorptionspectrum of amine terminated silicone used as a raw compound inPreparation Example 1, sulfonamide compound (A-1) prepared inPreparation Example 1 and glycidyl sulfonamide compound (A-1),respectively.

FIGS. 4, 5 and 6 are diagrams showing the results of proton nuclearmagnetic resonance spectrum of amine terminated silicone used as a rawcompound in Preparation Example 1, sulfonamide compound (A-1) andglycidyl sulfonamide compound (A-1), respectively.

DETAILED DESCRIPTION

The present invention relates to (1) a novel glycidyl sulfonamidecompound (A) represanted by the general formula (I): ##STR1## whereineach R¹ is a univalent hydrocarbon group having 1 to 20 carbon atoms,each R² is a bivalent hydrocarbon group having 1 to 6 carbon atoms, eachR³ is a univalent hydrocarbon groups having 1 to 6 carbon atoms, n is Oor an integer of 1 to 70 and X is a hydrogen atom or a glycidyl group,

(2) the process for preparing the glycidyl sulfonamide compound (A)represented by the general formula (I) comprising the steps of:subjecting a sulfonamide compound represented by the general formula(II): ##STR2## wherein each R¹ is a univalent hydrocarbon group having 1to 20 carbon atoms, each R² is a bivalent hydrocarbon group having 1 to6 carbon atoms and each R³ is a univalent hydrocarbon group having 1 to6 carbon atoms, Ω is O or an integer of 1 to 70, to an addition reactionwith an epihalohydrin and reacting the reaction mixture with a causticalkali,

(3) an epoxy resin composition, particularly, an epoxy resin coatingcomposition comprising (A) the above-mentioned glycidyl sulfonamidecompound represented by the general formula (I), (B) an epoxy resin and(C) an agent for curing epoxy resins, and (4) a cured product thereof.

The above-mentioned glycidyl sulfonamide compound (A) is contained inthe composition in order to improve flexibility and surface property ofthe cured product, particularly, the cured film.

The glycidyl sulfonamide compound (A) of the present invention can beprepared, for instance, according to a method described in Japanesepatent application No. 161505/1987, and the like

In the first step of the process for preparing the glycidyl sulfonamidecompound (A), the sulfonamide compound (II) is prepared. That is, as astarting compound, an amine-modified silicone represented by the generalformula (III): ##STR3## wherein each R² is a bivalent hydrocarbon grouphaving 1 to 6 carbon atoms, each R³ is a univalent hydrocarbon grouphaving 1 to 6 carbon atoms, and n is 0 or an integer of 1 to 70, issubjected to condensation reaction with a sulfonyl chloride representedby the general formula (IV):

    R.sup.1 SO.sub.2 Cl                                        (IV)

wherein R¹ is a univalent hydrocarbon group having 1 to 20 carbon atomsin the presence of a dehydrochlorination agent or a condensing agentsuch as sodium hydroxide to give the sulfonamide compound represented bythe above-mentioned general formula (II), having a (poly)siloxane mainchain of the molecule.

The amine modified silicone represented by the general formula (III)forms a main chain of the glycidyl sulfonamide compound (A) of thepresent invention. It is necessary that the amine-modified silicone(III) has at least one, preferably 5 to 70 siloxane bond, and hasaminoalkyl groups having 1 to 6 carbon atoms at both ends of themolecule. The substituent on the silicon atom is not limited so long asit is a hydrocarbon group having 1 to 6 carbon atoms. An amine-modifiedsilicone wherein the above-mentioned substituent is methyl group, ethylgroup, phenyl group, or the like is most general and easily available.Examples of the amine modified silicone are, for instance,1,3-bis(4-aminobutyl)tetramethyldisiloxane,1,3-bis(4-aminopropyl)tetramethyldisiloxane, and the like, in addition,a silicone oligomer in which both ends of the molecule are modified withamines (hereinafter referred to as "amine terminated silicone oligomer")available from CHISSO CORPORATION under the trade name of "SILAPLANE",and these are suitably employed. The amine modified siliconesrepresented by the general formula (III) can be used alone or inadmixture thereof.

Examples of the sulfonyl chloride represented by the general formula(IV) are, for instance, aliphaticsulfonyl chloride such asmethanesulfonyl chloride (corresponding to the compound, wherein R¹represents methyl group), ethanesulfonyl chloride (R¹ : ethyl group);aromaticsulfonyl chloride such as benzenesulfonyl chloride (R¹ : phenylgroup), o- or p- toluenesulfonyl chloride (R¹ : tolyl group), 2,4- or2,5-dimethylbenzenesulfonyl chloride (R¹ :dimethylphenyl group) and 1-or 2- naphthalenesulfonyl chloride (R¹ : naphthyl group); and the like.Among them, the aromatic sulfonyl chlorides are easily available asindustrial sources. The sulfonyl chloride represented by the generalformula (IV) can be used alone or in admixture thereof.

The used amount of the sulfonyl chloride represented by the generalformula (IV) is from 0.9 to 1.1 equivalents, preferably from 0.95 to1.05 equivalents, more preferably 1.0 equivalent per amine equivalent ofthe amine modified silicone represented by the general formula (III).When the amount of the sulfonyl chloride (III) is outside of theabove-mentioned range, the epoxy equivalent of the glycidyl sulfonamidecompound (A) obtained by the following reaction is increased, which isnot preferable.

As the condensing agent, a caustic alkali is preferably used, since itis available at a low price. It is preferable that the condensing agentis used in an amount of the same equivalent as the sulfonyl chloridefrom the viewpoints of the purity and yield of the product.

The condensation reaction can be carried out in the absence of solvent,however, it is preferable that an inactive solvent such as an aromatichydrocarbon or a halogenated hydrocarbon is used as the solvent forcontrolling the viscosity of the reaction mixture and temperature of thereaction system.

The condensation reaction of the first step of the process is usuallycarried out at a temperature of 0° to 70° C. for 1 to 2 hours, then anionic impurity is removed from the reaction mixture, and the reactionsolvent is distilled away in case of using it. The obtained product canbe used in the second step of the process as it is.

The second step of the process is that the sulfonamide compound (III)having (poly)siloxane in the main chain of the molecule obtained in thefirst step is subjected to addition reaction with an epihalohydrin.

Examples of the epihalohydrin are, for instance, epichlorohydrin,β-methylepichlorohydrin, epibromohydrin, epiiodohydrin, and the like.Epichlorohydrin is preferable since it can be industrially easilyobtained. The amount of the epihalohydrin is one or more equivalents persulfonamide group of the sulfonamide compound. It is preferable that theamount is from 2 to 10 equivalents per sulfonamide group of thesulfonamide to inhibit the side reaction.

The addition reaction proceeds very slowly or hardly proceeds in theabsence of the catalyst. Accordingly, it is very preferable that atleast one phase-transfer catalyst selected from the group consisting ofquaternary ammonium salt, quaternary phosphonium salt and quaternaryarsonium salt is used. Examples of such phase-transfer catalysts are,for instance, tetramethylammonium chloride, tetraethylammonium bromide,triethylmethylammonium chloride, triphenylmethylphosphonium chloride,tetraphenylphosphonium chloride and the like. The amount of thephase-transfer catalyst can be selected in the range of 0.01 to 100% bymole, preferably 1 to 10% by mole, based on the sulfonamide compound.The reaction temperature and the period of time for the additionreaction depend upon the amount of the catalyst used. Usually, thereaction is carried out at 70° to 120° C. for 0.5 to 12 hours,preferably at 100° to 110° C. for 3 to 8 hours.

The third step of the process is that the caustic alkali is added to theproduct obtained by the addition reaction of the second step, and themixture is subjected to dehydrohalogenation reaction. The phase-transfercatalyst used in the addition reaction can be used as the catalyst forthe dehydrohalogenation reaction. As the caustic alkali, sodiumhydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide,barium hydroxide, or the like can be used. Among them, sodium hydroxideis preferable since it is easily available as an industrial source. Thecaustic hydroxide can be used in the form of a solid or an aqueoussolution. The aqueous solution of the caustic hydroxide is preferablebecause it can be easily handled. The amount of the caustic alkali isfrom 1.0 to 2.0 equivalents, preferably from 1.1 to 1.5 equivalentsbased on the sulfonamide group. The dehydrohalogenation reaction iscarried out at 20° to 70° C. for 10 minutes to 3 hours, preferably at40° to 60° C. for 0.5 to 2.0 hours.

The dehydrohalogenation reaction is usually carried out in theepihalohydrin. The excess amount of the epihalohydrin can be optionallydistilled away and recovered prior to the reaction. In this case, it ispreferable that inactive solvent, for instance, ketones such as methylethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatichydrocarbons such as benzene, toluene and xylene; or halogenatedhydrocarbons such as chloroform and methylene chloride is used as adiluent of the glycidyl sulfonamide compound.

After the reaction is completed, the produced salt is removed from thereaction mixture by filtering, centrifuging or washing with water, andthen the unreacted epihalohydrin or the inactive solvent is distilledaway to give a glycidyl sulfonamide compound (A) of the presentinvention.

The glycidyl sulfonamide compound (A) has the general formula (I):##STR4##

In the general formula (I), R¹ is a univalent hydrocarbon group having 1to 20 carbon atoms. Examples of the hydrocarbon group R¹ are, forinstance, aliphatic hydrocarbon groups such as methyl group, ethylgroup, n-propyl group and isopropyl group; aromatic hydrocarbon groupssuch as phenyl group, tolyl group, dimethylpheuyl group, naphthyl group,o-, m- or p- cumenyl group and mesityl group; and the like. Among them,the compounds having methyl group, ethyl group, phenyl group, tolylgroup, dimethylphenyl group, naphthyl group or the like as R¹ in theformula (I) are preferable because the raw material of the compounds areeasily available. The compound having the aromatic hydrocarbon groupsuch as phenyl group, tolyl group, dimethylphenyl group or naphthylgroup as R¹ is more preferable since the raw material of the compound iseasily available as industrial source. When the compound has theunivalent hydrocarbon group having more than 20 carbon atoms as R¹, theraw material of the compound is not easily available.

In the general formula (I), R² is a bivalent hydrocarbon group having 1to 6 carbon atoms. Examples of the hydrocarbon group R² are, forinstance, methylene group, ethylene group, trimethylene group,tetramethylene group, and the like. Among them, the compound havingtrimethylene group as R² is preferable because the raw material of thecompound is easily available.

In the general formula (I), R³ is a unlvalent hydrocarbon group having 1to 6 carbon atoms. Examples of the hydrocarbon group R³ are, forinstance, methyl group, ethyl group, phenyl group, and the like. Thecompound having the group as R³ is more preferable because the rawmaterial of the compound is easily available.

In the general formula (I), n is 0 or an integer of 1 to 70. Thecompound represented by the general formula (I) wherein n is an integerof 4 to 65 is more preferable because the compound and the epoxy resincan form a suitable phase separation structure. When n is an integer ofmore than 70, the compound is completely separated from the epoxy resin,so it is very difficult to be dispersed uniformly it into the epoxyresin.

In the general formula (I), X is hydrogen atom or glycidyl group.Generally, the glycidyl sulfonsmide compound (A) represented by thegeneral formula (I) is a mixture of the compound (A) having the formula(I) wherein X is hydrogen and the compound (A) having the formula (I)wherein X is glycidyl group. A conversion of N--H in the sulfonamideinto glycidyl group is defined as "degree of epoxidation". The degree ofepoxidation is preferably not less than 70%, more preferably not lessthan 80%. The compound having a low degree of epoxidation is poor instorage stability and is easily increased in viscosity.

In the general formula (I), the number of each R¹ and R² is 2. Thegroups R¹ are the same or different and the group R² are the same ordifferent. In the general formula (I), the number of R³ is 2n+4, and thegroups R³ are the same or different. The compound having the formula (I)in which two R³ groups are the same and (2n+4) R³ groups are the same iseasily available.

Examples of the glycidyl sulfonamide compound (A) represented by thegeneral formula (I) are, for instance, a compound represented by thegeneral formula: ##STR5## wherein R², R³, n and X are as defined above,a compound represented by the general formula: ##STR6## wherein R², R³,n and X are as defined above, a compound represented by the generalformula: ##STR7## wherein R¹, R³, n and X are as defined above, and thelike. As further concrete examples of the compound (A), compoundsrepresented by the following general formulae (i) to (iv) areexemplified. ##STR8## wherein n is an integer of 5 to 20 ##STR9##wherein n is an integer of 5 to 20.

Among them, the glycidyl sulfonamide compound represented by the generalformula (ii) and the glycidyl sulfonamide compound represented by thegeneral formula (iv) are preferable because the raw materials of thesecompounds can be easily obtained.

The thus obtained glycidyl sulfonamide compound (A) is colorless orlight yellow liquid and has a low viscosity (about 1 to 50P) at roomtemperature. With respect to the glycidyl sulfonamide compound (A), itcan be confirmed that the glycidyl group is introduced into its moleculeby the experimental results of an absorption band of 905 to 930 cm⁻¹ ofinfrared absorption spectrum, a characteristic absorption of 2.5 to 4.0ppm of proton nuclear magnetic resonance spectrum and determination ofepoxy equivalent weight by hydrochloric acid-pyridine method.

The glycidyl sulfonamide compound (A) obtained in the above-mentionedprocess can be cured together with the curing agent (C), alike usualepoxy resins. The obtained cured product is elastic. The curing agent(C) is not limited so long as a curing agent is usually used when curingepoxy resins. Examples of the curing agent (C) are, for instance, acidanhydrides such as tetrahydrophthalic anhydride,methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride,methylhexahydrophthalic anhydride, nadic methyl anhydride, pyromelliticanhydride, trimellitic anhydride and benzophenonetetracarboxylic acidanhydride; acylic aliphatic polyamines such as diethylenetriamine andtriethylenetetramine; alicyclic amines such as menthenediamine andisophoronediamine; aromatic polyamines such as (m- or p-)xylylenediamine, (m- or p-) phenylenediamine,4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl sulfone; tertiaryamines such as benzyldimethylamine and2,4,6-tris(dimethylaminomethyl)phenol; polyamides; imidazoles such as2-methylimidazole and 2-ethyl-4-methylimidazole; Lewis acid-aminecomplex typified by boron trifluorideamine complex; dicyandiamide andits derivatives; polyphenols such as cresol novolak, phonol novolak,polyvinylphenol and primary condensation product of phenol-formaldehyde;polymercaptans; and the like. Among these curing agents (C), the agentwhich is in liquid state at room temperature is more preferable becauseit is easy to handle.

The glycidyl sulfonamide compound (A) of the present invention can beoptionally mixed and co-cured together with the other epoxy compound.The kind of the epoxy compound to be mixed with the compound (A) is notlimited, and mixing ratio of the glycidyl sulfonamide compound (A) andthe epoxy compound can be suitably adjusted.

The epoxy resin composition or the epoxy resin coating composition ofthe present invention comprises the glycidyl sulfonamide compound (A)represented by the general formula (I), an epoxy resin (B) and a curingagent (C).

The epoxy resin composition or the epoxy resin coating composition ofthe present invention can contain two or more kinds of the glycidylsulfonamide compounds (A).

The above-mentioned epoxy resin (B) is an epoxy resin having not lessthan 2 epoxy groups in its molecule, and preferably having the epoxyequivalent weight of 100 to 700 g/equivalent.

Examples of the epoxy resin (B) are, for instance, glycidyl amine epoxyresins prepared from amines such as 4,4'- or3,4'-diaminodiphenylmethane, m- or p-aminophenol, aminonaphthol andm-xylylenediamine (for instance, available from TOHTO KASEI CO., LTD.under the trade name of "YH-434", or from Sumitomo Chemical Company,Limited under the trade name of "ELM-120"); epibis type epoxy resins(for instance, available from Yuka Shell Epoxy Co., Ltd. under the tradename of "Epikote 807, 828 or 1001"); epi-bis type epoxy resins havingbrominated aromatic nucleus (for instance, available from TOHTO KASEICO., LTD. under the trade name of "YDB-400"); novolak epoxy resins suchas glycidyl derivatives of phenol novolak and glycidyl derivative ofcresol novolak (for instance, available from NIPPON KAYAKU CO., LTDunder the trade name of "EOCN-102"); polyglycidyl ether epoxy resinstypified by novolak epoxy resin having brominated aromatic nucleus;polyglycidyl esters of acids such as phthalic acid,cyclohexanedicarboxylic acid and the like; heterocyclic epoxy resinssuch as hydantoin epoxy resin and triglycidyl isocyanurate; andalicyclic epoxy resins. The above-mentioned epoxy resins can be usedalone or in admixture thereof. Among these epoxy resins, the epi-bistype epoxy resins are preferable from the viewpoint that the resins havewell-balanced properties, and the glycidyl amine epoxy resins arepreferable from the viewpoint that the resins have excellent thermalresistance. Especially, it is preferable that the epoxy resin (B) is anepoxy resin having at least one N,N-diglycidylamino group in onemolecule, such as tetraglycidyldiaminodiphenylmethane and/or acondensation product thereof because the defect that the cured coatingfilm prepared by the epoxy resin is too hard and brittle, can beremarkably improved by adding the glycidyl sulfonamide compound (A)represented by the general formula (I) into the resin.

In case of using the glycidyl sulfonamide compound (A) with the epoxyresin (B), the weight ratio of the compound (A) to the epoxy resin (B)is not limited. It is preferable that the weight ratio of the compound(A) to the resin (B) from 0.01:99.99 to 50:50, more preferably from0.1:99.9 to 20:80. The weight ratio can be selected depending on itsuse.

In case of using the above-mentioned glycidyl sulfonamide compound (A)together with the epoxy resin (B), a curing agent for curing epoxyresins (C) can be used without any limitation. There are exemplified, asthe curing agent (C), the same curing agents used in the case that theglycidyl sulfonamide compound (A) of the present invention is curedwithout being mixed with the epoxy resin (B). That is, examples of thecuring agent (C) are, for instance, acid anhydrides such astetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride,hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadicmethyl anhydride, pyromellitic anhydride, trimellitic anhydride andbenzophenonetetracarboxylic acid anhydride; chain aliphatic polyaminessuch as diethylenetriamine and triethylenetetramine; alicyclic aminessuch as menthenediamine and isophoronediamine; aromatic polyamines suchas (m- or p-) xylylenediamine, (m- or p-) phenylenediamine,4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl sulfone; tertiaryamines such as benzyldimethylamine and2,4,6-tris(dimethylaminomethyl)phenol; polyamides; imidazoles such as2-methylimidazole and 2-ethyl-4-methylimidazole; Lewis acid-aminecomplex typified by boron trifluoride-amine complex; dicyandiamide andits derivatives; polyphenols such as cresol novolak, phenol novolak,polyvinylphenol and primary condensation product of phenol-formaldehyde;polymercaptans; and the like.

Among these curing agents, the aromatic polyamide having at least 2primary amine groups in the molecule, such as 4,4'- or3,4'-diaminodiphenylsulfone or 4,4'- or 3,4'-diaminodiphenylmethane ispreferable since the cured product is excellent in thermal resistance;the aliphatic amine curing agent is preferable since the composition canbe cured quickly even at a low temperature; and the acid anhydride ispreferable since the cured product is excellent in thermal resistanceand electric property.

In case of using the epoxy resin composition of the present invention asa paint which can be cured without heating, it is preferable that thealiphatic amine curing agent is used as the curing agent since thecomposition can be cured at a low temperature, accordingly, at a roomtemperature. In case of using the epoxy resin composition as a paintwhich can be cured with heating, it is preferable that the aromaticamine curing agent or acid anhydride curing agent is used as the curingagent since the cured film having excellent film properties (such asthermal resistance and durability) can be obtained.

The amount of the curing agent (C) depends on the kind of the curingagent (C), it is preferable that the curing agent (C) is used in anamount known as the most suitable amount of the curing agent. Forinstance, in case of using the aliphatic (poly)amine curing agent, theallcyclic (poly)amine curing agent, aromatic (poly)amine curing agent orthe polyphenol, the agent is preferably used in an amount of 0.8 to 1.2equivalents, more preferably 0.9 to 1.1 equivalents based on oneequivalent of the total of epoxy groups of the glycidyl sulfonamidecompound (A) and the epoxy group of the epoxy resin (B). In case ofusing acid anhydride curing agent, the agent is preferably used in anamount of 0.7 to 1.0 equivalent, more preferably 0.8 to 0.9 equivalentbased on one equivalent of the total of epoxy groups of the glycidylsulfonamide compound (A) and the epoxy group of the epoxy resin (B). Acoating film having an excellent property can be obtained by using thecuring agent in such an amount. Further, in case of using the tertiaryamine, the imidazole, the Lewis acid-amine complex or the dicyandiamideas the curing agent, the agent can be used in an amount of 1 to 10 partsbased on 100 parts of the glycidyl sulfonamide compound (A) and theepoxy resin (B). A cured product having an excellent property can beobtained by using the curing agent in such an amount.

The epoxy resin composition or the epoxy resin coating composition ofthe present invention may contain, as occasion demands, variousadditives such as an accelerator used for improving the curing rate ofthe composition; a thermoplastic resin used for improving the propertyof cured product or film in an amount within a range which does notdeteriorate the properties of the composition; a monomer used inthermosetting resin or a thermosetting resin other than the epoxy resinused for controlling the curing rate and for improving the property ofthe film; a filler used for decreasing curing shrinkage; a couplingagent used for improving adhesive property against a substrate; anorganic or inorganic pigment for coloring; an organic solvent used foradjusting the viscosity of the composition; a reinforcement; a levelingagent; a fire retardant; and a stabilizer.

Examples of the above-mentioned accelerator are, for instance, tertiaryamines such as benzyldimethylamine and2,4,6-tris(dimethylaminomethyl)phenol; imidazole; and the like.

Examples of the above-mentioned thermoplastic resin which is generallyemployed are, for instance, xylene resin, ketone resin,dicyclopentadiene resin, and the like.

As for the above-mentioned monomer used in the thermosetting resin orthe thermosetting resin other than the epoxy resin, a monomer or a resinwhich can be cured together with the composition of the presentinvention is preferable. Examples of the monomer or the resin are, forinstance, unsaturated polyester resins, vinyl monomers, and the like.

Examples of the above-mentioned filler are, for instance, silica, talc,and the like.

Examples of the above-mentioned reinforcement are, for instance, glassfiber, carbon fiber, aramid fiber, and the like.

The epoxy resin composition of the present invention is usually preparedby mixing at once the glycidyl sulfonamide compound (A), the epoxy resin(B), the curing agent (C) and, if necessary, the other components.

When it is difficult to mix these components uniformly, the compositioncan be prepared by previously dissolving the components into an inactivesolvent to mix, then removing the solvent.

In order to improve the uniformity of the cured product, previously anadduct is prepared by reacting the glycidyl sulfonamide compound (A)with the curing agent (C) and then to the adduct is added the epoxyresin (B) to give the composition of the present invention.

The thus prepared composition can be cured at a room temperature, and inorder to obtain a cured product having excellent thermal resistance, itis preferable that the composition is finally heated at a temperature of100° to 200° C. for 1 to 5 hours. The thus obtained cured product can befurther improved in the thermal resistance by further post-curing theproduct at a temperature of 150° to 250° C.

The cured product usually is cloudy and has a structure having microdispersed (poly)siloxane in the resin.

Since the epoxy resin composition of the present invention contains, asthe component, the glycidyl sulfonamide compound (A) having a(poly)soloxane main chain and after curing the composition, it forms amicro phase separation as a rubber component, the cured product of theepoxy resin composition is remarkably improved in toughness incomparison with cured products of conventional epoxy resin composition.

When usual flexibilizers are employed, it is necessary that theflexibilizers are used in an amount of 10 to 20 parts based on 100 partsof the total amount of the epoxy resin and the flexibilizer. When usingthe flexibilizer, the thermal resistance of the cured productdeteriorates in exchange for flexibility. In the epoxy resin compositionof the present invention, however, even though the glycidyl sulfonamidecompound (A) is used in the same as or more than the amount ofconventional flexibilizers, the thermal resistance of the cured materialis little lowered. Further, even though the glycidyl sulfonamidecompound (A) is used in a small amount such as 5 parts or less based on100 parts of the total amount of the epoxy resin (B) and the compound(A), the mechanical properties of the cured material such as flexuralstrength and Izod impact strength can be remarkably improved withoutsubstantial deterioration of the thermal resistance thereof.

Since the glycidyl sulfonamide compound (A) of the present invention hasthe above-mentioned excellent properties which cannot be obtained inusual epoxy resins or flexibilizers, the compound (A) is useful as, forinstance, casting materials for electric or electronic apparatuses,adhesive agents, matrix materials for laminated materials or FRP.Especially, since the glycidyl sulfonamide compound (A) has bothexcellent thermal resistance and toughness and is effective indecreasing internal stress of the cured product, it is expected to beused in a field of materials to which mechanical or thermal stresses arerepeatedly given.

The epoxy resin coating composition of the present invention is usuallyprepared by mixing the glycidyl sulfonamide compound (A), the epoxyresin (B), the curing agent (C) and, if necessary, the other componentsin a suitable vessel with a stirrer such as brabender, kneader or mixer,and are mixed together. In such a case, the adding or mixing order ofthe components is not limited, and the components can be mixed at once.During the mixing procedure, the temperature of the composition issuitably adjusted, and usually the mixing is carried out at atemperature of 0° to 50° C. The thus prepared composition is applied bya spray, coater or brush, and is cured to give a film. The curingreaction can proceed at a room temperature, however, in order to obtaina cured film having excellent thermal resistance, it is preferable thatit is cured, for instance, at a temperature of 80° to 200° C.

When the glycidyl sulfonamide compound (A) is used together with theepoxy resin (B), since the glycidyl sulfonamide compound (A) has aglycidyl group in the molecule, the mixture of the compounds (A) and (B)can be cured by using the same curing agent as the curing agent for anepoxy resin, and the curing agent can be incorporated into the curingsystem.

With proceeding the curing reaction of the glycidyl sulfonamide compound(A) and the epoxy resin (B), in some cases, they form a structure havingphase separation in micron order, however, they do not bleed, since theyare chemically combined with each other.

The film prepared from the epoxy resin coating composition of thepresent invention is excellent in the properties such as toughness,flexibility, water repellency and lubrication.

The present invention is more specifically described and explained bymeans of the following Examples in which all parts are by weight unlessotherwise noted. It is to be understood that the present invention isnot limited to the Examples, and various changes and modification may bemade in the invention without departing from the spirit and scopethereof.

PREPARATION EXAMPLE 1

Preparation of sulfonamide compound (A-1)

A four necked flask having a volume of 200 ml was charged with 49.30 g(amino group:100 millimoles) of an amine terminated silicone oligomer(available from CHISSO CORPORATION under the trade name of "SILAPLANEFM-3311", amine equivalent: 493 g/equivalent, corresponding to thecompound represented by the general formula (III) wherein R², R³ and nrepresent trimethylene group, methyl group and an integer of 9 to 10,respectively. The identifying data are shown in FIG. 1 and FIG. 4. FIG.1 is a diagram showing the results of infrared adsorption spectrum ofthe amine terminated silicone (measurement range: 650 to 4000 cm⁻¹,measured neat). FIG. 4 is a diagram showing the results of protonnuclear magnetic resonance spectrum of the amine terminated silicon(NMR: 300 MHz, solvent: CDCl₃). In FIG. 1, the sharp absorption a₁ of IRat 2950 cm⁻² indicates --CH_(2/3) group, the strong absorption b₁ at1260 and 790 cm⁻¹ indicates Si--CH.sub. 3 group, the strong broadabsorption C₁ at 1020 to 1090 cm⁻¹ indicates ##STR10## group, and theweak broad absorption at 3400 cm⁻¹ indicates --NH₂. In FIG. 4, the largepeak signals near 0.10 to 0.20 indicate protons of ##STR11## and thesharp signal at 1.80 ppm indicates amino end group (a₄ and b₄ indicateintegral intensity and δ, respectively.), 20 ml of chloroform and 20 ml(100 millimoles) of 5N aqueous solution of sodium hydroxide. Into themixture, 17.66 g (100 millimoles) of benzenesulfonyl chloride was addeddropwise over 10 minutes with externally cooling with ice water. Then,the mixture was heated to 60° C., and was stirred for 2 hours. Waterlayer of the mixture was removed by decantation, and the chloroform wasdistilled away to give 63.15 g of a sulfonamide compound having asiloxane main chain of (hereinafter referred to as "sulfonamide compound(A-1)"). It was found from a material balance of the procedure that thereaction almost quantitatively proceeded. The sulfonamide compound (A-1)was a liquid compound having a low viscosity at a room temperature. Theidentifying data of the obtained sulfonamide compound (A-1) are shown inFIG. 2 and FIG. 5. FIG. 2 is a diagram showing the results of infraredadsorption spectrum of the sulfonamide compound (A-1) (measurementrange: 650 to 4000 cm⁻¹, measured: neat). FIG. 5 is a diagram showingthe results of proton nuclear magnetic resonance spectrum of thesulfonamide compound (A-1) (NMR: 300 MHz, solvent: CDCl₃). In FIG. 2,the newly appeared peaks of absorption of IR are a₂ at 3250 cm⁻¹ :##STR12## b₂ at 1155 and 1325 cm⁻¹ : ##STR13## c₂ at 690 and 750 cm⁻¹ :##STR14## respectively. In FIG. 5, the signals of near 7.55 and 7.88 ppmare corresponding protons in benzene ring and indicate monosubstitutedbenzene ##STR15## and the signal of 4.45 ppm indicates proton insulfonamide ##STR16## (a₅ and b₅ indicate integral intensity and δ,respectively).

PREPARATION EXAMPLE 2

Preparation of sulfonamide compound (A-2)

The same procedure as in Preparation Example 1 was repeated except that247.9 g of an amine terminated silicone oligomer EM-3321 (available fromCHISSO CORPORATION under the trade name "SILAPLANE FM-3321", amineequivalent: 2479 g/equivalent, corresponding to the compound representedby the general formula (III), wherein R², R³ and n representtrimethylene group, methyl group and an integer of 63 to 64,respectively, instead of the amine terminated silicone oligmer FM-3311to give 258.5 g of a sulfonamide compound having a siloxane main chainof the molecule (hereinafter referred to as "sulfonamide compound(A-2)").

The sulfonamide compound (A-2) was also a liquid compound having a lowviscosity.

EXAMPLE 1

Preparation of glycidyl sulfonamide compound (A-1)

To 63.15 g of the sulfonamide compound (A-1) prepared in PreparationExample 1, were added 46.3 g of epichlorohydrin and 1.14 g ofbenzyltriethyl ammonium chloride (catalyst for reaction), then themixture was reacted at 100° to 110° C. for 4 hours. The reaction mixturewas cooled to 50° C., and 120.0 ml of 5N aqueous solution of sodiumhydroxide was added to the reaction mixture dropwise over 10 minuteswith stirring violently. After the addition, the mixture was furtherstirred for 2 hours. The water layer of the mixture containing salts wasremoved by decantation, and the organic layer was washed 4 times with100 ml of deionized water. The excess epichlorohydrin was distilled awayunder reduced pressure to give 68.23 g of a glycidyl sulfonamidecompound (hereinafter referred to as "glycidyl sulfonamide compound(A-1)") (corresponding to the compound represented by the generalformula (I) wherein R¹, R², R³ and n represent a phenyl group, atrimethylene group, a methyl group and an integer of 11 to 12,respectively). With respect to the glycidyl sulfonamide compound (A-1),the viscosity was 2.8 poise at 25° C., the epoxy equivalent weightdetermined by means of hydrochloric acid-pyridine method was 729. Thedegree of epoxidation calculated from the epoxy equivalent weight was94.5% and the yield based on the theoretical yield was 99.0%.

The identifying data of the obtained glycidyl sulfonamide compound (A-1)are shown in FIG. 3 and FIG. 6. FIG. 3 is a diagram showing the resultsof infrared absorption spectrum of the glycidyl sulfonamide compound(A-1) (measurement range: 650 to 4000 cm⁻¹, measured: neat). FIG. 6 is adiagram showing the results of proton nuclear magnetic resonancespectrum of the glycidyl sulfonamide compound (A-1) (NMR: 300 MHz,solvent: CDCl₃).

The peak a₂ at 3250 cm⁻¹ : ##STR17## in FIG. 2 disappears at a₃ in FIG.3 and the peak b₃ at 930 cm⁻¹ : ##STR18## newly appeares in FIG. 3 incomparison with FIG. 2, which indicates that the proton of sulfonamideis substituted by a glycidyl group. In FIG. 6, the signal of 4.45 ppm:sulfonamide proton disappeares and the characteristic signals of 2.5 to4.0 ppm newly appear, in comparison with FIG. 5. Near 2.5 to 4.0 ppm,besides the signals of 5 protons of glycidyl group, the signals of twoprotons of methylene group next to the nitrogen in formula (m) appear atthe same place. The ratio of the integral intensity of the signals of2.5 to 4.0 ppm to that of the protons of benzene ring is about 7:5,which indicates that the above identification of the glycidylsulfonamide compound is valid (a₆ and b₆ indicate integral intensity andδ, respectively). ##STR19##

With respect to the obtained glycidyl sulfonamide compound (A-1), thesolubility in solvents at a room temperature and the compatibility withepoxy resins were investigated. The results are shown in Table

                  TABLE 1                                                         ______________________________________                                        [Solubility of glycidyl sulfonamide compound (A-1)]                           ______________________________________                                        Solvent  Methanol    Chloroform                                                                              Ethyl acetate                                  Solubility                                                                             ⊚                                                                          ⊚                                                                        ⊚                               Solvent  Toluene     Ethyl ether                                              Solubility                                                                             ⊚                                                                          ⊚                                         Solvent  M1BK    n-Hexan  Water  Ep828.sup.1                                                                         TGDDM.sup.2                            Solubility                                                                             ⊚                                                                      ⊚                                                                       X      X     X                                      ______________________________________                                         ⊚ The compound is soluble in the solvent at suitable ratio     X The compound is not soluble in, or not compatible with the solvent.         .sup.1 Available from Yuka Shell Epoxy Co., Ltd, under the trade name of      "Epikote 828", epoxy equivalent weight: 189                                   .sup.2 Tetraglycidyldiaminodiphenylmethane, epoxy equivalent weight: 120 

EXAMPLE 2

Preparation of glycidyl sulfonamide compound (A-2)

The same procedure as in Preparation Example 1 was repeated except that258.5 g of the sulfonamide compound (A-2) prepared in PreparationExample 2 was used instead of 63.15 g of the sulfonamide compound (A-1)to give 247.0 g of a glycidyl sulfonamide compound (hereinafter referredto as "glycidyl sulfonamide compound (A-2)"). The glycidyl sulfonamidecompound (A-2) was also a liquid compound having a low viscosity at aroom temperature and had an epoxy equivalent weight of 2978.

EXAMPLE 3

To 10.0 parts of the glycidyl sulfonamide compound (A-1) prepared inExample 1, was added 26.91 parts of 4,4'-diaminodiphenylmethane(hereinafter referred to as "DDM"), and the mixture was heated at 120°C. to melt and then was stirred for 10 minutes. Further, 100 parts ofEpikote 828 (an epi-bis type epoxy resin having an epoxy equivalentweight of 189, available from Yuka Shell Epoxy Co., Ltd.) was added tothe mixture. The mixture was mixed with heating to give a varnish, whichwas casted into a space between two glass plates set with inserting aspacer having a thickness of 3 mm. The thus molded varnish was curedwith heating at 80° C. for 2 hours, at 120° C. for 2 hours, at 180° C.for 1 hour and then at 200° C. for 4 hours to give a cured bulkymaterial.

The obtained cured bulky material was cut into test pieces havingdesired sizes by using a diamond cutter. The test pieces were subjectedto measurements of heat distortion temperature (hereinafter referred toas "HDT"), bending test, Izod impact test without notch, and pressurecooker test (hereinafter referred to as "PCT") at 120° C. and 2atmospheres for 8 hours. The condition of pre-treatments of the testpieces and the method of measurements of properties of the material werecarried out according to the method provided in JIS K 6911. With respectto the cured bulky material, the flexural strength and flexuralelasticity were 9.2 kg/mm² and 287.4 kg/mm², respectively. The materialhaving such properties as above can be sufficiently employed as acoating film.

COMPARATIVE EXAMPLE 1

A cured material was prepared in the same procedure as in Example 3except that 100 parts of Epikote 828 and 26.23 parts of the DDM weremixed with heating to give a varnish. Then, the properties of theobtained cured material were measured.

COMPARATIVE EXAMPLE 2

A cured material was prepared in the same procedure as in Example 3except that 100 parts of Epikote 828, 10 parts of a polypropyleneglycoldiglycidylether (available from ASAHI DENKA KOGYO K.K. under thetrade name of "ED 506", epoxy equivalent weight: 291) and 27.93 parts ofDDM were mixed with heating to give a varnish. Then, the properties ofthe obtained cured material were measured in the same manner as inExample 3.

COMPARATIVE EXAMPLE 3

A cured material was prepared in the same procedure as in Example 3except that 100 parts of the Epikote 828, 10 parts of apolyethyleneglycoldiglycidylether (available from Nippon Oil and FatsCo., Ltd. under the trade name of "E-100", epoxy equivalent weight: 142)and 29.72 parts of DDM were mixed with heating to give a varnish. Then,the properties of the obtained cured material were measured in the samemanner as in Example 3.

COMPARATIVE EXAMPLE 4

A cured material was prepared in the same procedure as in Example 3except that 100 parts of Epikote 828, 25.22 parts of DDM and 10 parts ofthe amine-modified silicone oligomer (available from CHISSO CORPORATIONunder the trade name of "SILAPLANE FM-3311", amine equivalent: 493g/equivalent) were mixed with heating to give a varnish. Then, theproperties of the obtained cured material were measured in the samemanner as in Example 3.

With respect to the above-mentioned Example 3 and Comparative Examples 1to 4, the amounts of constituents of the composition, the curingconditions and the results of measurements of the physical properties ofthe obtained cured materials are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________             Composition (parts)                                                                      Glycidyl sulfonamide                                      Ex. No.  Epikote 828*.sup.1                                                                   DDM compound (A-1)                                                                           ED-506*.sup.2                                                                      E-100*.sup.3                                                                       FM-3311*.sup.4                       __________________________________________________________________________    3        100.0  26.91                                                                             10.0       --   --   --                                   Comp. Ex. No. 1                                                                        100.0  26.23                                                                             --         --   --   --                                   Comp. Ex. No. 2                                                                        100.0  27.93                                                                             --         10.0 --   --                                   Comp. Ex. No. 3                                                                        100.0  29.72                                                                             --         --   10.0 --                                   Comp. Ex. No. 4                                                                        100.0  25.22                                                                             --         --   --   10.0                                 __________________________________________________________________________             Properties of cured bulky materials                                                       Bending test                                                                           Modulus of                                                           Flexural strength                                                                      flexural elasticity                             Ex. No.  HDT (°C., 18.5 kg/cm.sup.2)                                                        (kg/mm.sup.2)                                                                          (kg/mm.sup.2)                                                                          Elongation (%)                         __________________________________________________________________________    3        158.4       9.2      287.4    5.1                                    Comp. Ex. No. 1                                                                        168.3       10.4     351.2    4.8                                    Comp. Ex. No. 2                                                                        138.7       11.3     335.9    5.1                                    Comp. Ex. No. 3                                                                        145.2       11.8     364.9    4.9                                    Comp. Ex. No. 4                                                                        152.8        8.9     289.5    5.0                                    __________________________________________________________________________                Properties of cured bulky materials                               Ex. No.     Izod impact test (kg.cm/cm)                                                                  Water absorption after PCT (%)                     __________________________________________________________________________    3           35.9           1.76                                               Comp. Ex. No. 1                                                                           20.2           1.66                                               Comp. Ex. No. 2                                                                           24.9           1.97                                               Comp. Ex. No. 3                                                                           21.1           1.95                                               Comp. Ex. No. 4                                                                           26.9           2.02                                               __________________________________________________________________________     [Notes                                                                        *.sup.1 Epibis type epoxy resin, available from YukaShell Epoxy Co., Ltd.     *.sup.2 Polypropylene glycol diglycidyl ether, available from ASAHI DENKA     KOGYO K.E.                                                                    *.sup.3 Polyethylene glycol diglycidyl ether, available from Nippon Oil       and Fats Co., Ltd.                                                            *.sup.4 Aminemodified silicone oligomer, available from CHISSO CORPORATIO     *.sup.5 Izod impact test without notch                                   

EXAMPLE 4

The varnish prepared in Example 3 was applied onto a glass plate byusing a bar coater to give a coating film having a thickness of 100 μm.The coating film was cured in the same conditions as in Example 3 andcontact angle of the cured film to a waterdrop was measured. The resultsare shown in Table 3. The coefficient of dynamic friction between theobtained coating film and mirror polished SUS plate was measuredaccording to the method provided in ASTM-D-1894-63. The results areshown in Table 3. The measurement was carried out by using a load cellat a pressure between the SUS plate and the cured film of 24 g/cm² andhead speed of 50 mm/minute.

COMPARATIVE EXAMPLE 5

The same procedure as in Example 4 was repeated except that the varnishprepared in Comparative Example 1 was used to give a coating film. Then,the properties of the coating film were measured in the same manner asin Example 4. The results are shown in Table 3.

COMPARATIVE EXAMPLE 6

The same procedure as in Example 4 was repeated except that the varnishprepared in Comparative Example 2 was used to give a coating film. Then,the properties of the coating film were measured in the same manner asin Example 4. The results are shown in Table 3.

COMPARATIVE EXAMPLE 7

The same procedure as in Example 4 was repeated except that the varnishprepared in Comparative Example 3 was used to give a coating film. Then,the properties of the coating film were measured in the same manner asin Example 4. The results are shown in Table 3.

COMPARATIVE EXAMPLE 8

The same procedure as in Example 4 was repeated except that the varnishprepared in Comparative Example 4 was used to give a coating film. Then,the properties of the coating film were measured in the same manner asin Example 4. The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Properties of coating films                                                           Contact angle of                                                              coating film  Coeffecient of dynamic friction                         Ex. No. to a waterdrop θ (°)                                                           (.sup.μ κ)                                     ______________________________________                                        4       78.3           0.21                                                   Comp.   64.3           0.21                                                   Ex. No. 5                                                                     Comp.   74.7           0.26                                                   Ex. No. 6                                                                     Comp.   57.0           0.25                                                   Ex. No. 7                                                                     Comp.   48.3           0.27                                                   Ex. No. 8                                                                     ______________________________________                                    

EXAMPLE 5

To 1.0 part of the glycidyl sulfonamide compound (A-1) was added 41.03parts of DDM, and the mixture was heated 120° C. to melt and then wasstirred for 10 minutes. Further, 100 parts of tetraglycidyldiaminodiphenylmethane (epoxy equivalent weight: 121, hereinafterreferred to as "TGDDM") was added to the mixture. The mixture was mixedwith heating to give a varnish, which was casted into a space betweentwo glass plates set with inserting a spacer having a thickness of 3 mm.The molded varnish was cured with heating at 80° C. for 2 hours, at 120°C. for 2 hours, at 180° C. for 1 hour and then at 200° C. for 4 hours togive a cured bulky material.

The obtained cured bulky material was cut into test pieces havingdesired sizes by using a diamond cutter. The test pieces were subjectedto measurements of HDT, bending test, Izod impact test without notch.The results are shown in Table 4. The procedures of the pre-treatment ofthe test pieces and the measurement of properties of the cured materialwere carried out according to the method provided in JIS K 6911.

EXAMPLES 6 AND 7

A cured material was prepared in the same procedure as in Example 5except that 2.0 parts (Example 6) or 5.0 parts (Example 7) of theglycidyl sulfonamide compound (A-1) was added to 100 parts of TGDDM,then a prescribed amount of DDM was added to each of the mixture to giveeach varnish. The properties of the each cured material were measured.The results are shown Table 4.

COMPARATIVE EXAMPLE 9

A cured material was prepared in the same procedure as in Example 5except that 100 parts of TGDDM and 40.97 parts of DDM were mixed withheating to give a varnish. The properties of the obtained cured materialmatter were measured in the same manner as in Example 5. The results areshown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________             Composition (parts)                                                                Glycidyl                                                                      sulfonamide                                                     Ex. No.  TGDDM                                                                              compound (A-1)                                                                         DDM Condition of curing                                __________________________________________________________________________    Comp. Ex. No. 9                                                                        100.0                                                                              0        40.97                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                         5        100.0                                                                              1.0      41.03                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                         6        100.0                                                                              2.0      41.10                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                         7        100.0                                                                              5.0      41.30                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                         __________________________________________________________________________              Results of tests                                                                        Flexural                                                                             Flexural      Izod impact strength                           HDT       strength                                                                             elasticity                                                                           Elongation                                                                           without notch                        Ex. No.   (°C., 18.5 kg/cm.sup.2)                                                          (kg/mm.sup.2)                                                                        (kg/mm.sup.2)                                                                        (%)    (kg · cm/cm)                __________________________________________________________________________    Comp. Ex. No. 9                                                                         238.8     11.1   401.6  3.3    10.5                                 5         238.8     13.3   429.5  4.7    22.5                                 6         238.0     13.4   411.3  4.8    14.7                                 7         236.5     12.7   406.5  3.5    12.7                                 __________________________________________________________________________

EXAMPLE 8

A cured material was prepared in the same procedure as in Example 5except that 2.0 parts of the glycidyl sulfonamide compound (A-1), 26.36parts of DDM and 100 parts of Epikote 828 (an epi-bis type epoxy resinavailable from Yuka Shell Epoxy Co., Ltd., epoxy equivalent weight: 189)were mixed with heating to give a varnish. The properties of the curedmaterial were measured in the same manner as in Example 5. The resultsare shown in Table 5.

EXAMPLES 9 TO 11

A cured material was prepared in the same procedure as in Example 8except that 5.0 parts (Example 9), 10.0 parts (Example 10) or 20.0 parts(Example 11) of the glycidyl sulfonamide compound (A-1) was added to 100parts of Epikote 828, then a prescribed amount of DDM was added to eachof the mixture to give each varnish. The properties of the each curedmaterial were measured in the same manner as in Example 8. The resultsare shown in Table 5.

COMPARATIVE EXAMPLE 10

A cured material was prepared in the same procedure as in Example 5except that 100 parts of Epikote 828 and 26.23 parts of DDM were mixedwith heating to give a varnish. The properties of the cured materialwere measured in the same manner as in Example 5. The results are shownin Table 5.

                                      TABLE 5                                     __________________________________________________________________________             Composition (parts)                                                                 Glycidyl                                                                      sulfonamide                                                    Ex. No.  Epikote 828                                                                         compound (A-1)                                                                         DDM Condition of curing                               __________________________________________________________________________    Comp. Ex. No. 10                                                                       100.0 0        26.23                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                         8       100.0 2.0      26.36                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                         9       100.0 5.0      26.57                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                        10       100.0 10.0     26.91                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                        11       100.0 20.0     27.59                                                                             At 80° C. for 2 hours, at 120°                                  C. for 2 hours,                                                               at 180° C. for 1 hour and then at                                      200° C. for 4 hours                        __________________________________________________________________________              Results of tests                                                                         Flexural                                                                             Flexural      Izod impact strength                          HDT        strength                                                                             elasticity                                                                           Elongation                                                                           without notch                       Ex. No.   (°C., 18.5 kg/cm.sup.2)                                                           (kg/mm.sup.2)                                                                        (kg/mm.sup.2)                                                                        (%)    (kg · cm/cm)               __________________________________________________________________________    Comp. Ex. No. 10                                                                        168.3      10.4   351.2  4.81   20.2                                 8        165.4      10.8   311    7.0    56.3                                 9        159.8      10.2   303    6.3    53.0                                10        158.4      9.2    287.4  5.1    35.9                                11        141.2      8.5    244    6.1    30.7                                __________________________________________________________________________              Results of tests                                                                           Loss in weight at                                                Initiation Temperature                                                                     initiation temperature                                                                     Temperature at                                      of           of           Loss in weight                                                                        Loss in weight                              thermal decomposition*                                                                     thermal decomposition*                                                                     of 10%* at 500° C.*                Ex. No.   (°C.) (%)          (°C.)                                                                          (%)                               __________________________________________________________________________    Comp. Ex. No. 10                                                                        378          1.1          379     55.1                               8        377          0            379     65.9                               9        374          0.4          379     53.9                              10        367          0.6          373     57.8                              11        372          1.7          374     61.0                              __________________________________________________________________________     *Results of thermogravimetric analysis by means of a TGA apparatus of         RTGDTA type (II) made by RIGAKU DENKI Co., Ltd. Rate of raising               temperature: 10° C./minute, set temperature: room temperature to       500° C., under N.sub.2 gas atmosphere                             

The glycidyl sulfonamide compound (A) of the present invention having a(poly)siloxane main chain in its molecule has much lower viscosity thanthat of usual epoxy resins and provides a flexible cured material havinglarge elongation. The glycidyl sulfonamide compound (A) can beoptionally mixed and co-cured with any other epoxy compound, andthereby, it becomes possible to impart flexibility and toughness to thecured material of the epoxy resin. When a glycidyl compound of(poly)oxyalkylene is used as a flexibilizer for epoxy resins, theproperties of the cured material of the epoxy resins such as thermalresistance, chemical resistance and water absorption deteriorate.However, when the glycidyl sulfonamide compound (A) of the presentinvention is used, the impact strength of the cured material of theepoxy resin can be remarkably improved with controlling deterioration ofthe thermal resistance of the cured material to a minimum.

As mentioned above, since the glycidyl sulfonamide compound (A) of thepresent invention has excellent properties which cannot be found inusual epoxy resins or flexibilizers, the compound (A) is useful as, forinstance, casting materials for electric or electronic apparatuses,paints, adhesive agents, matrix materials for laminated materials orFRP, and the like. Especially, since the glycidyl sulfonamide compound(A) brings both excellent thermal resistance and toughness to theconventional epoxy resins, and is effective in decreasing internalstress of the cured material, the compound (A) is expected to be used inthe field of materials to which mechanical or thermal stresses should berepeatedly given.

With respect to the cured material of the epoxy resin composition of thepresent invention, the properties such as flexural strength, elongationand Izod strength can be remarkably improved since the epoxy resincomposition contains the glycidyl sulfonamide compound (A).Deterioration of mechanical properties and thermal resistance of thecured material other than the above-mentioned properties is very small,therefore, there is not caused any problem in the practical usesthereof. The epoxy resin composition of the present invention canprovide a cured material having both excellent toughness and thermalresistance, while conventional epoxy resins cannot provide a curedmaterial having both toughness and thermal resistance at the same time.

Furthermore, because the resin composition for epoxy paint of thepresent invention contains the glycidyl sulfonamide compound (A) havinga (poly)siloxane main chain of the molecule and the compound (A)contributes, as a rubber like component, to absorption of impact force,water repellency and lubrication on the surface of the cured material ofthe composition, the resin composition for an epoxy paint of the presentinvention has effects to provide an excellent coating film having highermechanical strength, softness, water repellency and lubrication, and ismore excellent in flexibility in comparison with conventional epoxyresin paints. Generally, when a glycidyl compound of (poly)oxyalkyleneis used as a flexibilizer for paint, there occur deteriorations ofproperties such as increase of water absorption, increase of coefficientof friction and decrease of thermal resistance of the coating film.However, when the epoxy resin composition of the present invention isused for a paint, the deteriorations of the above-mentioned propertiesof the coating film can be controlled in such a low level that problemsare hardly caused. Further, there is not caused bleed of the glycidylsulfonamide compound (A).

The epoxy resin composition of the present invention is useful aspaints, coating materials for electric or electronic apparatuses, or thelike since the composition provides a coating film having excellentproperties which cannot be found in conventional epoxy resin paints, asmentioned above.

What is claimed is:
 1. A glycidyl sulfonamide compound represented bythe formula (I): ##STR20## wherein each R¹ is a monovalent hydrocarbongroup having 1 to 20 carbon atoms, each R² is a bivalent hydrocarbongroup having 1 to 6 carbon atoms, each R³ is a monovalent hydrocarbongroup having 1 to 6 carbon atoms, n is 0 or an integer of 1 to 70 and Xis hydrogen atom or glycidyl group.
 2. The glycidyl sulfonamide compoundof claim 1, wherein R¹ is phenyl group.
 3. The glycidyl sulfonamidecompound of claim 1, wherein R¹ is methyl group.
 4. The glycidylsulfonamide compound of claim 1, wherein R² is trimethylene group. 5.The glycidyl sulfonamide compound of claim 1, wherein R³ is methylgroup.